Carbon Disulfide → 2-Iodo-4-octylbenzenethiol

HRID 717728Notes

Reaction equation

HRID 717728 reaction equation
[I:1][C:2]1[CH:8]=[C:7]([CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[CH:6]=[CH:5][C:3]=1N.N([O-])=O.[Na+].[OH-].[K+].C(=S)=[S:24]>Cl.O.CCO>[I:1][C:2]1[CH:8]=[C:7]([CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])[CH:6]=[CH:5][C:3]=1[SH:24]

Participants

8

Reactant 4

HCID 6348Carbon DisulfideHCID 14797Potassium Hydroxide2×HCID 121652542-Iodo-4-octylanilineHCID 23668193Sodium Nitrite

Product 1

HCID 666151462-Iodo-4-octylbenzenethiolYield 24%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolvent2×HCID 962WaterSolvent2×

Conditions

Temperature
55 °C

Procedure

To a stirred mixture of the product of Step A (0.4 g; 1.21 mmol) in 35% HCl (0.2 ml) an ice cold solution of NaNO2 (0.1 g, 1.3 mmol) in H2O (1 ml) was added at 0° C., followed by a solution of K-ethylxhanthate, freshly prepared by rapid stirring of a mixture of KOH (0.085 g, 1.5 mmol) and CS2 (0.173 g, 1.5 mmol) in a mixture of EtOH and H2O (1 ml:1.5 ml) for 2.5 h at room temperature. The resulting mixture was stirred for 5 h at 55° C., than cooled to room temperature and extracted with EtOAc (50 ml). The organic layer was separated, washed with H2O, dried over MgSO4 and filtered. The filtrate was evaporated and the residue was diluted to 20 ml with EtOH and KOH (0.5 g, 3.62 mmol) was added. This was stirred for 5 h at reflux and the mixture was evaporated to dryness and the residue was treated with 1M HCl and extracted with EtOAc (20 ml). The organic layer was separated, dried over MgSO4 and filtered. The filtrate was evaporated and the residue was purified by FCC (SiO2; hexane/EtOAc) to give the title compound (0.1 g, 24%), as a yellow paste, which was used as such in next step. 1H NMR (CDCl3) 7.75 (b, 1H); 7.28 (d, 1H, J=7.95 Hz); 7.00 (dd, 1H, J=7.95, 2.0 Hz); 7.02 (s, 1H); 2.51-2.45 (m, 2H); 1.53 (b, 2H); 1.25 (b, 10H); 0.86 (t, 3H, J=6.42 Hz).

Workup

  1. additionwas added at 0° C.
  2. customfreshly prepared
  3. temperaturethan cooled to room temperature
  4. extractionextracted with EtOAc (50 ml)
  5. customThe organic layer was separated
  6. washwashed with H2O
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. customThe filtrate was evaporated
  10. additionwas added
  11. stirringThis was stirred for 5 h
  12. temperatureat reflux
  13. customthe mixture was evaporated to dryness
  14. additionthe residue was treated with 1M HCl
  15. extractionextracted with EtOAc (20 ml)
  16. customThe organic layer was separated
  17. dry with materialdried over MgSO4
  18. filtrationfiltered
  19. customThe filtrate was evaporated
  20. customthe residue was purified by FCC (SiO2; hexane/EtOAc)

Sources & evidence

ORD record
ord-281d59027f6944e6aee3ee0746c7f87b
Source dataset
uspto-grants-2015_11
Patent number
US09193716B2

Reaction notes

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